CN119144237B - Modified epoxy-cerium oxide polishing solution and preparation method thereof - Google Patents
Modified epoxy-cerium oxide polishing solution and preparation method thereof Download PDFInfo
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- CN119144237B CN119144237B CN202411663761.5A CN202411663761A CN119144237B CN 119144237 B CN119144237 B CN 119144237B CN 202411663761 A CN202411663761 A CN 202411663761A CN 119144237 B CN119144237 B CN 119144237B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/1409—Abrasive particles per se
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Abstract
The invention provides a modified epoxy-cerium oxide polishing solution and a preparation method thereof, wherein the modified epoxy-cerium oxide polishing solution is mainly prepared from, by mass, 0.2% -0.5% of modified cerium oxide abrasive, 0.02% -0.35% of stabilizer, 0.25% -0.4% of ammonia water and 99.08% -99.2% of deionized water, wherein the modified cerium oxide abrasive is prepared by mixing cerium oxide and epoxy carboxylic acid in a mass ratio of (20:1) - (200:1). The epoxy-cerium oxide polishing solution can enable the abrasive to be dispersed in the solution more uniformly, improves the uniformity of the suspension, and can keep the suspension property (D50) for up to 2 months under the condition of ensuring the removal rate.
Description
Technical Field
The invention belongs to the technical field of rare earth materials, and particularly relates to a modified epoxy-cerium oxide polishing solution and a preparation method thereof.
Background
Chemical Mechanical Polishing (CMP) is a critical technique used in the fabrication of silicon wafers to achieve surface planarization to meet the requirements of high precision and high density integration of semiconductor devices. Cerium oxide (CeO 2) is a key polishing material and has been widely used in silicon wafer polishing processes due to its unique physicochemical properties.
The polishing effect of cerium oxide is mainly derived from its excellent chemical reactivity and mechanical polishing ability. In the polishing process, the cerium oxide particles can form an oxide layer through chemical reaction with the silicon surface, and the oxide layer is removed through mechanical friction, thereby achieving a planarization effect. In addition, the particle structure of cerium oxide can provide higher polishing rate, has lower defect generation rate, and can improve polishing efficiency on the premise of ensuring flatness.
However, the conventional cerium oxide polishing material has problems in application, such as difficulty in controlling the balance of polishing rate and surface defects, and easiness in occurrence of particle agglomeration during use, poor suspension stability, and thus, influence of polishing uniformity. Therefore, how to improve the suspension stability of cerium oxide particles while securing the removal rate thereof by improving the preparation process, surface modification or dispersion technique thereof has become a hot spot of current research.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the invention is to provide a modified epoxy-cerium oxide polishing solution, which enhances the dispersibility and chemical stability of the abrasive, enhances the chemical stability of cerium oxide, reduces the dissolution or passivation of particles caused by chemical reaction in the polishing process, prolongs the service life of the abrasive, and further enhances the suspension stability of the abrasive while not affecting the removal rate by adding a stabilizer and a pH regulator.
The second aim of the invention is to provide the preparation method of the modified epoxy-cerium oxide polishing solution, which can lead the particle size of the prepared cerium oxide to be more uniform, is convenient for modification of epoxy carboxylic acid groups, has simple preparation steps, obviously saves the manufacturing cost, is convenient for mass production, has green preparation process, reduces environmental pollution and meets the requirements of green chemistry.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a modified epoxy-cerium oxide polishing solution which is mainly prepared from the following raw materials in percentage by mass:
0.2% -0.5% of modified cerium oxide abrasive;
0.02% -0.35% of stabilizer;
0.25% -0.40% of ammonia water;
99.08 to 99.2 percent of deionized water;
wherein the modified cerium oxide abrasive is prepared by mixing cerium oxide and epoxy carboxylic acid in a mass ratio of (20:1) - (200:1).
In the invention, the cerium oxide abrasive is modified by using the epoxy carboxylic acid, and the carboxyl of the epoxy carboxylic acid and the polishing surface can form a weak chemical bond, so that the interaction force of the cerium oxide and the silicon surface (the polished object) is improved, and the polishing rate and the surface smoothness are further improved. The cerium oxide abrasive modified by the epoxy carboxylic acid group has stronger dispersibility, is beneficial to reducing the agglomeration phenomenon of particles in the polishing solution, thereby ensuring the uniformity of the abrasive in the polishing process and reducing the surface defects.
The micro stabilizer can eliminate foam generated in the preparation process, increase the viscosity of the polishing solution, improve the suspension stability of the polishing solution, ensure the polishing efficiency of products, and simultaneously can assist epoxy carboxylic acid to stabilize cerium oxide abrasive materials, reduce the generation of surface defects, remarkably improve the quality and flatness of the surface of a silicon wafer polished by using the polishing solution, and meet the requirements of high-precision manufacturing processes.
In the invention, the mass ratio between the epoxy carboxylic acid and the cerium oxide is limited, and experiments show that when the epoxy carboxylic acid is used for modifying and connecting the cerium oxide, the 1:1 connection between the modifier and the cerium oxide cannot be achieved, that is, the epoxy carboxylic acid cannot modify all cerium oxide contained in the system due to the influence of steric hindrance or electrostatic repulsive force, and only partial modification can be achieved, so that the optimal ratio between the modifier and the cerium oxide is required to be found in the modification process so as to achieve the optimal modification effect.
Experiments are carried out to adjust, and when cerium oxide and epoxy carboxylic acid are mixed in a mass ratio of (20:1) - (200:1), particularly under the condition that the content of cerium oxide is a multiple of the content of epoxy carboxylic acid, although only partial cerium oxide performance is changed, intermolecular acting force exists between modified cerium oxide abrasive particles and common cerium oxide abrasive particles, aggregation tendency among cerium oxide particles can be reduced, and the abrasive can be uniformly dispersed in a system for a long time, so that the change of physicochemical properties of polishing liquid is realized. When the mass of the epoxy carboxylic acid is large, not only the efficiency of the connection between the cerium oxide and the modifier cannot be improved, waste is caused, but also the physicochemical properties of the cerium oxide may be affected. If the cerium oxide is excessive, the content of the modified cerium oxide is too small, which results in a decrease in the dispersibility thereof and a failure to stably disperse for a long period of time.
Preferably, as a further specific embodiment, the cerium oxide and the epoxy carboxylic acid are present in a mass ratio= (40:1) - (100:1).
Preferably, as a further specific embodiment, the cerium oxide and the epoxy carboxylic acid are present in a mass ratio=100:1 or 50:1.
As mentioned above, the polishing liquid prepared under the condition that the content of cerium oxide is a multiple of the content of epoxy carboxylic acid is better, and further experimental screening shows that the performance of the polishing liquid is improved more obviously in the range of (20:1) - (200:1) which is close to 100:1 and 50:1. Therefore, in the actual preparation process, the cerium oxide and the epoxy carboxylic acid are in a mass ratio of (100:1) or (50:1), so that the performance of the finally prepared polishing solution can be effectively ensured, and waste is avoided.
Preferably, as a further specific embodiment, the particle size of the cerium oxide is 200nm to 400nm.
The polishing performance of the cerium oxide abrasive is highly dependent on the size and shape of the cerium oxide abrasive, and the chemical polishing performance of the oxide monotonically increases with the particle size of the cerium oxide abrasive, so that the selection of the particle size of the cerium oxide is more prone to selecting cerium oxide particles with large particle size as a reaction raw material, but the selection of the particle size of the cerium oxide is not suitable to be too large or too small in view of steric hindrance or intermolecular interaction force, or the dispersion performance of the finally prepared polishing solution is influenced.
Preferably, as a further specific embodiment, the epoxycarboxylic acid is any one or more of cis epoxysuccinic acid, epoxyethylformic acid, 2, 3-epoxyethane dicarboxylic acid or trans epoxysuccinic acid;
the stabilizer is one or more of polyvinyl alcohol, polyethylene glycol, polydimethylsiloxane, polyethylene oxide, polypropylene oxide, carboxymethyl cellulose, sodium polyacrylate or hydroxyethyl methyl cellulose.
The polishing solution can realize polishing principle that Ce-O-Si bonds are formed, part of polishing abrasive materials which are currently known in the market can introduce metal ions and an oxidant in the preparation process, the oxidant can oxidize Ce 3+ into Ce 4+, and Ce 4+ has better polishing performance, and the metal ions can damage the formed Ce-O-Si bonds in the polishing process, so that the polishing performance is reduced. Therefore, although the polishing performance can be improved by introducing metal ions and an oxidant, the polishing performance is presumably limited by negative influence of the metal ions on Ce-O-Si bonds, and partial physical properties of the prepared polishing solution are difficult to break through.
In the invention, the selected epoxy carboxylic acid and stabilizer can realize the modification of cerium oxide under the condition of not introducing metal ions, reduce the influence of the metal ions on the polishing performance of the formed polishing solution, and simultaneously the stabilizer can effectively improve other physical properties of the polishing solution and ensure that the polishing performance is not influenced.
Preferably, as a further specific embodiment, the epoxy carboxylic acid is cis-epoxy succinic acid and epoxy ethyl formic acid are mixed in a mass ratio of (1-3): 1;
the stabilizer is polyvinyl alcohol, polydimethylsiloxane and carboxymethyl cellulose which are mixed according to the mass ratio of (1-3) to 1:1.
Preferably, as a further specific embodiment, the cis-epoxysuccinic acid and epoxyethylformic acid are mixed in a mass ratio of 1:1;
the stabilizer is polyvinyl alcohol, polydimethylsiloxane and carboxymethyl cellulose which are mixed according to a mass ratio of 2:1:1.
As can be seen from the experimental results, when the epoxy carboxylic acid is cis-epoxy succinic acid and epoxy ethyl formic acid are mixed in the mass ratio of (1-3): 1, the improvement of the performance of the polishing solution is more favorable when the ratio is preferably 1:1, and the influence between intermolecular interaction forces is presumed to be possible, so that the modification effect is increased. And when the polyvinyl alcohol, the polydimethylsiloxane and the carboxymethyl cellulose are mixed according to the mass ratio of (1-3) to 1:1, the polishing solution can be defoamed, thickened and stabilized, and when the polyvinyl alcohol, the polydimethylsiloxane and the carboxymethyl cellulose are mixed according to the mass ratio of 2:1:1, the suspension stability and the dispersibility of the polishing solution can be ensured.
Preferably, as a further specific embodiment, the pH adjuster is aqueous ammonia.
In the invention, metal ions are not introduced in the reaction process, so that the pH regulator containing the metal ions is not selected in the selection of the pH regulator, while ammonia gas dissolved in water can generate NH 4 + ions, but the influence of the metal ions on the physical properties of the polishing solution is small, and the metal ions are easy to eliminate. The polishing agent system needs to be adjusted to an alkaline environment with ph=10-12 during the preparation process, so as to improve the suspension stability.
The invention also provides a preparation method of the modified epoxy-cerium oxide polishing solution, which comprises the following steps:
Preparing cerium oxide, and mixing the cerium oxide with deionized water to form uniform slurry;
Grinding the slurry, separating to obtain a grinding medium, and freeze-drying the grinding medium to obtain a cerium oxide abrasive;
Dispersing the polishing abrasive in deionized water, ultrasonically vibrating, adding epoxy carboxylic acid, mixing, heating, centrifuging, washing, and freeze-drying to obtain a modified epoxy-cerium oxide abrasive;
mixing the epoxy-cerium oxide abrasive with deionized water, adding a pH regulator and a stabilizer, and performing ultrasonic dispersion to obtain the epoxy-cerium oxide abrasive.
When cerium oxide is mixed with deionized water to form a slurry, it is necessary to appropriately control the water content therein, and the amount of water added in this step is generally 3 to 5 times the mass of the cerium oxide abrasive to ensure good fluidity and dispersibility.
The drying modes used in the invention are freeze drying, and the freeze drying can ensure the drying efficiency and simultaneously freeze the grinding of the prepared grinding materials. And the pH regulator and the stabilizer are added at the end of the reaction, so that the long-time preservation of the polishing solution is facilitated, and the dispersibility and the suspension stability of the polishing solution can be improved.
Preferably, as a further specific embodiment, the temperature of the freeze-drying is-30 ℃ (-20 ℃);
the heating temperature is 70-100 ℃.
Under the condition of the solid content, the modified epoxy-cerium oxide is more beneficial to be dispersed in the ionized water. The optimal heating temperature is 80 ℃, and the optimal heating time is 12h.
Compared with the prior art, the invention has the beneficial effects that:
The chemical and physical properties of the cerium oxide abrasive are optimized through the modification of epoxy carboxylic acid and the addition of a stabilizer, the reactivity and the removal rate of the cerium oxide abrasive in the chemical mechanical polishing process can be improved, so that the polishing efficiency is effectively improved, a stable surface modification layer is formed through interaction with the surfaces of cerium oxide particles, the aggregation tendency among particles is reduced, the abrasive can be more uniformly dispersed in a solution, the uniformity of a suspension is improved, the surface is provided with hydrophilic groups, the solubility of the particles in the solution is improved, the sedimentation rate of the particles is reduced, and the stability time of the suspension is prolonged.
The modified cerium oxide nano abrasive prepared by the preparation method can keep the suspension property (D50) for up to 2 months under the conditions of no additive effect and removal rate guarantee.
Drawings
FIG. 1 is an X-ray diffraction image of an epoxy carboxylic acid modified ceria abrasive;
FIG. 2 is a thermogravimetric analysis image of an epoxy carboxylic acid modified ceria abrasive;
FIG. 3 is a transmission electron microscope image of an epoxy carboxylic acid modified ceria abrasive;
FIG. 4 is a scanning electron microscope image of an epoxy carboxylic acid modified ceria abrasive;
FIG. 5 is a photograph of a 1h suspension stability of an epoxy carboxylic acid modified ceria abrasive;
FIG. 6 is a 7 day suspension stability photograph of an epoxy carboxylic acid modified ceria abrasive;
FIG. 7 is a 15 day suspension stability photograph of an epoxy carboxylic acid modified ceria abrasive;
FIG. 8 is a photograph of 30-day suspension stability of an epoxy carboxylic acid modified ceria abrasive.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Step one, preparing cerium oxide
2000G of cerium carbonate was calcined in a rotary kiln at 600℃for 24 hours, and after grinding, cerium oxide having a particle size of 300nm was obtained.
Step two, modification
Mixing the prepared cerium oxide with deionized water with the mass of 5 times of that of the cerium oxide to form uniform slurry, uniformly adding the cerium oxide slurry into a grinding cavity of a sand mill, and filtering to separate out grinding media to obtain uniformly refined dispersion liquid. And (3) placing the dispersion liquid in a freeze dryer to carry out freeze drying at the temperature of minus 30 ℃ and grinding by using a mortar to obtain the cerium oxide abrasive.
5G of cerium oxide abrasive, 0.05g of a mixture of cis-epoxysuccinic acid and 0.05g of epoxyethyl formic acid, and 100mL of water were mixed in a 250mL round bottom flask and placed in a stirrer with oil bath heating, when the oil bath temperature reached 80 ℃ for starting timing, after reaction 12 h, the centrifuged solid was washed with deionized water and absolute ethanol, -20 ℃ for freeze drying, and grinding, respectively, to obtain a modified epoxy-cerium oxide abrasive (as shown in FIGS. 1-4, X-ray diffraction images, thermogravimetric images, transmission electron microscopy images, and scanning electron microscopy images of the modified epoxy-cerium oxide abrasive were clearly shown).
Step three, preparing polishing solution
Mixing 2.5g of the modified epoxy-cerium oxide abrasive and 500g of deionized water, dropwise adding 2g of ammonia water to adjust the pH to 11.5, simultaneously adding a mixture of 0.05g of polyvinyl alcohol, 0.025g of polydimethylsiloxane and 0.025g of carboxymethyl cellulose, and stirring for 30min after ultrasonic dispersion for 60min to obtain the polishing solution prepared by the abrasive.
The contents of the respective substances prepared under this condition are shown in Table 1:
TABLE 1 mass and percentage of the respective substances
。
Configuration of cerium oxide abrasive suspension and suspension test:
Accurately weighing 1.5 g (0.0001 g) of cerium oxide sample, placing in a 150mL beaker, adding a little water for beating, adding 30mL-40mL of water, transferring into a 50mL graduated flask, and adding water for dilution to the graduation. Transferring into a beaker, placing on an electric magnetic stirrer, stirring for 10min at room temperature, transferring into a cylindrical separating funnel, and standing at room temperature for 4 hours for later use. Placing 0.5g-1.0g of powder sample into a 50mL beaker containing 10mL of deionized water, ultrasonically dispersing in a water bath ultrasonic tank (proper amount of water is added in the ultrasonic tank in advance, and the water amount is proper to be just immersed in the sample solution in the beaker) for 20min, and immediately measuring.
After standing for 4 hours, the sample was pipetted into a 200mL volumetric flask to a scale by drawing 5mL of the suspension about 6mL below the surface of the upper portion of the cylindrical separating funnel. Then the piston was fully opened a second time to remove about 10mL of the lower suspension in a 50L beaker, 5mL of which was pipetted into a 200mL volumetric flask and diluted to the scale with water. The two samples were shaken well, the required milliliters were pipetted into 50mL volumetric flasks, and diluted to scale with acetone-water mixtures. Until the measured value is 50% of the initial value, the time at this time is recorded.
Example 2
The specific embodiment is the same as in example 1, and only the kind of the epoxy carboxylic acid is changed. Cis-epoxysuccinic acid, epoxyethylformic acid, 2, 3-epoxyethane dicarboxylic acid, trans-epoxysuccinic acid.
When no epoxy carboxylic acid was used, a CeO 2 sample was obtained;
when cis-epoxysuccinic acid was used, sample No.1 was obtained;
when using ethylene oxide formic acid, sample No. 2 was obtained;
when 2, 3-ethylene oxide dicarboxylic acid was used, sample No. 3 was obtained;
When trans-epoxysuccinic acid was used, sample No. 4 was obtained;
when the mass ratio of cis-epoxysuccinic acid to epoxyethylformic acid is 3:1, a sample No. 5 is obtained;
When the mass ratio of cis-epoxysuccinic acid to epoxyethylformic acid is 5:1, a sample No. 6 is obtained;
when the mass ratio of cis-epoxysuccinic acid to epoxyethylformic acid was used to be 0.5:1, sample No. 7 was obtained.
The D50 values were determined according to the suspension measurement experiments in example 1, and the experimental results are shown in Table 2.
TABLE 2 influence of different epoxy carboxylic acids on suspension properties of polishing solutions
。
From the experimental results, it can be seen that different epoxy carboxylic acids have an important influence on the suspension stability of the modified cerium oxide nano abrasive suspension. The suspension stability is best when the mass ratio of cis-epoxysuccinic acid to epoxyethylformic acid is 1:1, the suspension stability is slightly reduced when the cis-epoxysuccinic acid is excessive or the cis-epoxysuccinic acid is less in content, and the mass ratio of cis-epoxysuccinic acid to epoxyethylformic acid is 1:1 as the best ratio according to comprehensive experimental results. The epoxy carboxylic acid can be chemically bonded with hydroxyl on the surface of cerium oxide after surface hydroxylation, so that the suspension stability is greatly improved, and the excellent removal rate of the epoxy carboxylic acid can be ensured. The principle that the combination of cis-epoxysuccinic acid and epoxy ethyl formic acid improves the stability of the cerium oxide abrasive is supposed to be the influence of intermolecular acting force on cerium oxide.
Example 3
Specific embodiment the same as in example 1, only the ratio of epoxy carboxylic acid to cerium oxide nano abrasive was changed.
In this example, the epoxy carboxylic acid was mixed with the cis-epoxy succinic acid and the epoxy ethylformic acid in a mass ratio of 1:1, hereinafter abbreviated as CES, to finally obtain a polishing liquid CeO 2 @CES.
When the mass ratio of cerium oxide to epoxy carboxylic acid=200:1, 5g cerium oxide, 0.025gCES;
When the mass ratio of cerium oxide to epoxy carboxylic acid=100:1, 5g cerium oxide, 0.05gCES;
When the mass ratio of cerium oxide to epoxycarboxylic acid=50:1, 5g cerium oxide, 0.1gCES (example 1) was used;
when the mass ratio of cerium oxide to epoxy carboxylic acid=40:1, 5g cerium oxide, 0.125gCES;
When the mass ratio of cerium oxide to epoxy carboxylic acid=20:1, 5g cerium oxide, 0.4gCES;
The D50 values were determined according to the suspension measurement experiments in example 1, and the experimental results are shown in Table 3.
TABLE 3 influence of the different mass ratios of cerium oxide to epoxycarboxylic acid on the properties of the polishing solution
。
From the experimental data of example 3, it can be seen that at higher CES to ceria mass ratios (e.g., 100:1), the ceria surface is covered with more CES molecules, thereby providing more negative charge or functional group sites. The higher charge density can effectively enhance electrostatic repulsive force among particles, so that particle aggregation is reduced, and the stability of the suspension is improved. Meanwhile, CES molecules contain certain hydrophobic components, and stronger hydrophobic changes can occur along with the cerium oxide surface. This variation can inhibit agglomeration of the particles, allowing the particles to be more uniformly dispersed in the aqueous solution, thereby improving suspension stability.
Example 4
The embodiment is the same as in example 1, except that the particle size of cerium oxide is changed.
Scheme 1. Selecting cerium oxide with particle size of 200nm;
Scheme 2 selection of cerium oxide with particle size of 300nm
Scheme 3. The particle size of the cerium oxide is selected to be 400nm.
The experimental results are shown in table 4.
TABLE 4 influence of cerium oxide of different particle sizes on polishing properties and suspension stability of polishing solutions
。
Experimental data can show that the particle size of cerium oxide is in proper conditions, so that the polishing rate of the finally prepared polishing solution is moderate, and no obvious scratch exists. At the same time, larger or smaller particle sizes may lead to a decrease in suspension stability.
Example 5
The specific implementation procedure is the same as in example 1, and only the oil bath stirring heating temperature and heating time in the modification process are changed.
The D50 values were determined according to the suspension measurement experiments in example 1, and the experimental results are shown in Table 5.
TABLE 5 influence of different heating temperatures and heating times on suspension stability of polishing solutions
。
As can be seen from experimental data of example 5, different heating temperatures and heating times have an important effect on suspension stability of the polishing solution, and at a lower temperature (e.g., 60 degrees), the reaction rate may be slower, the modification effect of the epoxy carboxylic acid on the cerium oxide surface is insufficient, and the suspension improvement effect is not obvious. At a higher temperature (e.g., 100 degrees), the reaction rate is increased, but the molecular structure of the epoxy carboxylic acid may be changed or side reactions may occur, which may affect the modification effect and decrease the suspension property.
The longer the reaction time, the more the epoxy carboxylic acid contacts the surface of cerium oxide, the more fully modified, but over a certain period of time excessive modification may occur, resulting in increased surface instability, affecting the stability of the suspension. In the experiment, 12 hours is a moderate time, so that the epoxy carboxylic acid forms a stable modification layer on the surface of cerium oxide, and the best effect is achieved.
Example 6
The specific embodiment was consistent with example 1, with only the mass of each material being changed to change the percentage content, as shown in table 6,
TABLE 6 influence of the change in the ratio between substances on the suspension stability of the polishing liquid
。
As can be seen from the data in example 6, the change in the ratio has a certain influence on the suspension stability of the polishing liquid, specifically, the suspension stability of the polishing liquid is lowered, and the main reason is that the ratio of the modified cerium oxide abrasive is lowered, so that the ratio of the modified cerium oxide abrasive is lowered to a certain extent, and the performance is lowered. But in general, the variation in its performance is within the expected range.
Comparative example 1
The specific embodiment is consistent with example 1, only varying the mass ratio of cerium oxide to epoxy carboxylic acid mixture:
When the mass ratio of cerium oxide to epoxycarboxylic acid=250:1, 5g cerium oxide, 0.02g CES are used;
when the mass ratio of cerium oxide to epoxycarboxylic acid=10:1, 5g cerium oxide, 0.5g CES was used.
The specific experimental results are shown in table 7.
TABLE 7 influence of different mass ratios of cerium oxide to epoxycarboxylic acid on the properties of polishing solutions
。
Comparing the experimental data of comparative example 1 with that of example 3, it can be seen that the suspension stability is lowered when the mass ratio of cerium oxide to epoxy carboxylic acid is too large or too small, and that the connection efficiency between cerium oxide and epoxy carboxylic acid is lowered due to the excessive content of either substance, so that the components in the prepared polishing liquid are easily aggregated, thereby lowering the dispersion property thereof.
Comparative example 2
The polishing liquid was prepared by mixing cerium oxide with an oxidizing agent, and the specific embodiment was consistent with example 1, changing only the mass ratio of cerium oxide to oxidizing agent:
The oxidizing agent used in this example is hydrogen peroxide.
When the mass ratio of cerium oxide to oxidizing agent=10:1, 5g cerium oxide, 0.5g hydrogen peroxide, 0.5g CES are used;
When the mass ratio of cerium oxide to oxidizing agent=20:1, 5g cerium oxide, 0.25g hydrogen peroxide, 0.25g CES were used.
The specific experimental results are shown in table 8.
TABLE 8 influence of different mass ratios of cerium oxide to oxidizing agent on the properties of polishing solutions
。
The experimental measurement data show that the suspension property of CeO 2 nano particles in the polishing solution is greatly influenced by the addition of the oxidant, and meanwhile, the addition of the oxidant can react with epoxy carboxylic acid used for modification, so that the modification effect is weakened.
Experimental example 1 determination of polishing Rate of polishing liquid
Using samples 1-7 of example 2 and the modified epoxy-ceria abrasive prepared in example 1, 2.5g was uniformly dispersed in 500mL deionized water, and subjected to 30min of ultrasound to prepare a polishing solution. Samples 1 to 7 and CeO 2 in example 2 correspond to the polishing rates of samples 1 to 7 and CeO 2 in this experimental example. The above samples were polished on 1mm thick sheets of SiO 2, and the specific polishing rates for the abrasive samples modified with different epoxy carboxylic acids are shown in Table 9.
TABLE 9 influence of different epoxy carboxylic acid modifications on polishing rate of cerium oxide nano-abrasive
。
The different molecular structures of the epoxy carboxylic acid affect the chemical nature of the ceria surface, thereby altering the interaction between the particles and the SiO 2. Some epoxy carboxylic acids may enhance the friction or reactivity between the cerium oxide and the surface of the material, increasing the removal rate of the material, while others may reduce the active sites or reduce the interaction of the particles with the material, resulting in a reduced polishing rate.
From the experimental data in the experimental example, the invention can increase the suspension stability of the polishing solution under the condition of stabilizing the polishing rate, and has obvious technical progress.
Experimental example 2 measurement of suspension stability under prolonged standing
The modified epoxy-cerium oxide abrasive prepared in example 1 was taken to have the same mass as a commercially available common cerium oxide abrasive, and both were formulated into a polishing liquid having a solid content of 10%. The prepared polishing solution was allowed to stand in a laboratory, and images of the standing for 1h, 7 days, 15 days and 30 days were recorded, and the experimental results are shown in fig. 5 to 8. As can be seen from the figure, the polishing solution prepared by the method can be stably suspended for 30 days without precipitation aggregation, while the commercial polishing solution has obvious precipitation after standing for 7 days, and the solution is completely clear after 15 days, and the liquid is separated from the solid.
In the test of the experimental examples, the solid content is generally selected to be 0.5% -10% for measurement. The polishing solution prepared by the invention can be stably stored for a long time, and experiments prove that the suspension property (D50) of the polishing solution is up to 2 months.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (9)
1. The modified epoxy-cerium oxide polishing solution is characterized by being prepared from the following raw materials in percentage by mass:
0.2% -0.5% of modified cerium oxide abrasive;
0.02% -0.35% of stabilizer;
0.25% -0.40% of ammonia water;
99.08 to 99.2 percent of deionized water;
wherein, the modified cerium oxide abrasive is prepared by mixing cerium oxide and epoxy carboxylic acid in a mass ratio of (20:1) - (200:1);
the pH of the modified epoxy-ceria slurry is = 10-12;
the epoxy carboxylic acid is cis-epoxy succinic acid, 2, 3-ethylene oxide dicarboxylic acid
Or alternatively, the first and second heat exchangers may be,
The epoxy carboxylic acid is cis-epoxy succinic acid and epoxy ethyl formic acid which are mixed in a mass ratio of 1:1 or 0.5:1.
2. The modified epoxy-cerium oxide polishing liquid according to claim 1, wherein the cerium oxide and the epoxy carboxylic acid are mixed in a mass ratio= (40:1) - (100:1).
3. The modified epoxy-cerium oxide polishing liquid according to claim 2, wherein the mass ratio of cerium oxide to epoxy carboxylic acid is =100:1 or 50:1.
4. The modified epoxy-cerium oxide polishing liquid according to claim 1, wherein the particle size of the cerium oxide is 200nm to 400nm.
5. The modified epoxy-cerium oxide polishing liquid according to claim 1, wherein the stabilizer is one or more of polyvinyl alcohol, polyethylene glycol, polydimethylsiloxane, polyethylene oxide, polypropylene oxide, carboxymethyl cellulose, sodium polyacrylate or hydroxyethyl methyl cellulose.
6. The modified epoxy-cerium oxide polishing liquid according to claim 5, wherein the stabilizer is polyvinyl alcohol, polydimethylsiloxane and carboxymethyl cellulose, and the mixture is mixed in a mass ratio of (1-3): 1:1.
7. The modified epoxy-cerium oxide polishing liquid according to claim 6, wherein the stabilizer is polyvinyl alcohol, polydimethylsiloxane and carboxymethyl cellulose mixed in a mass ratio of 2:1:1.
8. A method for preparing the modified epoxy-cerium oxide polishing liquid according to any one of claims 1 to 7, comprising the steps of:
Preparing cerium oxide, and mixing the cerium oxide with deionized water to form uniform slurry;
Grinding the slurry, separating to obtain a grinding medium, and freeze-drying the grinding medium to obtain a cerium oxide abrasive;
Dispersing polishing abrasive materials in deionized water, ultrasonically vibrating, adding epoxy carboxylic acid, mixing and heating to 70-100 ℃ for 12 hours, centrifuging, washing, and freeze-drying to obtain modified epoxy-cerium oxide abrasive materials;
mixing the epoxy-cerium oxide abrasive with deionized water, adding a pH regulator and a stabilizer, and performing ultrasonic dispersion to obtain the epoxy-cerium oxide abrasive.
9. The method for preparing a modified epoxy-cerium oxide polishing liquid according to claim 8, wherein the temperature of freeze-drying is-30 ℃ to-20 ℃;
The temperature of the heating was 80 ℃.
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| KR20220157327A (en) * | 2021-05-20 | 2022-11-29 | 주식회사 엠피에스피 | Ceria particle for abrasive and slurry comprising the same |
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| JP5287174B2 (en) * | 2008-04-30 | 2013-09-11 | 日立化成株式会社 | Abrasive and polishing method |
| CN101475791B (en) * | 2009-01-20 | 2012-08-29 | 江苏工业学院 | Preparation and use of cerium oxide / silicon oxide compound abrasive |
| KR101180401B1 (en) * | 2009-09-23 | 2012-09-10 | 주식회사 엘지화학 | Slurry composition for chemical mechanical polishing and polishing method |
| CN102051127B (en) * | 2009-11-06 | 2014-04-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN105803583A (en) * | 2016-05-12 | 2016-07-27 | 安徽金叶碳素科技有限公司 | Rare earth carbon powder and preparation method thereof |
| JP7031485B2 (en) * | 2018-05-11 | 2022-03-08 | 昭和電工マテリアルズ株式会社 | CMP polishing agent and its manufacturing method, and CMP polishing method |
| CN116285895B (en) * | 2023-03-09 | 2024-11-12 | 上海大学 | Ethylenediaminetetraacetic acid grafted cerium oxide composite abrasive grain, preparation method and application thereof |
| CN117655937B (en) * | 2024-02-02 | 2024-04-26 | 四川江天科技有限公司 | Rare earth polishing disc for polishing crystal glass and preparation method thereof |
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| CN101096080A (en) * | 2007-06-29 | 2008-01-02 | 南京航空航天大学 | Consolidated abrasive grinding and polishing pad with self-correcting function and preparation method |
| KR20220157327A (en) * | 2021-05-20 | 2022-11-29 | 주식회사 엠피에스피 | Ceria particle for abrasive and slurry comprising the same |
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